CN116965169A - Perovskite solar cell, photovoltaic module - Google Patents
Perovskite solar cell, photovoltaic module Download PDFInfo
- Publication number
- CN116965169A CN116965169A CN202180094972.XA CN202180094972A CN116965169A CN 116965169 A CN116965169 A CN 116965169A CN 202180094972 A CN202180094972 A CN 202180094972A CN 116965169 A CN116965169 A CN 116965169A
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- Prior art keywords
- hole transport
- transport layer
- electrode
- solar cell
- optionally
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/84—Layers having high charge carrier mobility
- H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
- H01L31/107—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier working in avalanche mode, e.g. avalanche photodiodes
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Abstract
The application provides a perovskite solar cell and a photovoltaic module. The perovskite solar cell further comprises a first hole transport layer and a second hole transport layer, wherein the first hole transport layer is positioned between the second hole transport layer and the light absorption layer, and the second hole transport layer is positioned between the first electrode and the light absorption layer, or the second hole transport layer is positioned between the second electrode and the light absorption layer. The first hole transport material of the first hole transport layer is selected from one of PTAA and nickel oxide doped or undoped by a first doping element, and the second hole transport material of the second hole transport layer comprises at least one of a P-type transition metal oxide semiconductor material and a P-type transition metal halide semiconductor material which can isolate water and oxygen.
Description
The application belongs to the technical field of solar cells, and particularly relates to a perovskite solar cell and a photovoltaic module.
With the development of modern industry, global energy shortage and environmental pollution problems are increasingly highlighted, and solar cells are receiving more and more attention as ideal renewable energy sources. A solar cell, also known as a photovoltaic cell, is a device that converts light energy directly into electrical energy by a photoelectric or photochemical effect. Improving the photoelectric conversion efficiency of solar cells has been the direction of efforts by researchers. Perovskite (perovskie) solar cells, which use Perovskite materials as light absorbing layers, rapidly acquire high photoelectric conversion efficiency within several years after birth, have received attention in recent years. The perovskite material absorbs incident sunlight and then excites to generate electron-hole pairs, and then the electron-hole pairs are separated into electrons and holes and transported to the cathode and the anode respectively. How to accelerate the transport of holes and prevent the recombination of electrons and holes is important to improve the photoelectric conversion efficiency of perovskite solar cells.
Disclosure of Invention
The application aims to provide a perovskite solar cell and a photovoltaic module, which aim to improve the hole extraction and transmission efficiency of a hole transmission layer, improve the open voltage and current of the perovskite solar cell and improve the photoelectric conversion efficiency and the service life of the perovskite solar cell.
The first aspect of the application provides a perovskite solar cell, which comprises a first electrode, a second electrode and a light absorption layer arranged between the first electrode and the second electrode, wherein the perovskite solar cell further comprises a first hole transmission layer and a second hole transmission layer, the first hole transmission layer is arranged between the second hole transmission layer and the light absorption layer, the second hole transmission layer is arranged between the first electrode and the light absorption layer, or the second hole transmission layer is arranged between the second electrode and the light absorption layer. The first hole transport material of the first hole transport layer is selected from one of PTAA and nickel oxide doped or undoped by a first doping element, and the second hole transport material of the second hole transport layer comprises at least one of a P-type transition metal oxide semiconductor material and a P-type transition metal halide semiconductor material which can isolate water and oxygen.
In the perovskite solar cell, the first hole transport material is close to the light absorption layer, so that holes in the light absorption layer can be extracted efficiently. The second hole transport material has better surface wettability and better film forming property, thereby being beneficial to improving the bonding strength between the whole hole transport layer and the electrode. The second hole transport material can also form a passivation protection layer on the surface of the first hole transport layer so as to passivate the surface of the first hole transport layer and prevent the first hole transport material from being denatured or degraded due to contact with air; meanwhile, the passivation protection layer can also isolate water and oxygen and prevent the water and oxygen from corroding the first hole transport material, so that the extraction and transport capacity of the first hole transport material to holes can be better exerted. The second hole transport material can also improve the overall conductivity of the hole transport layer, thereby further improving the extraction and transport efficiency of holes. The second hole transport material has fewer internal defects in the crystal and can also block further migration of charged halogen ions, thereby improving the stability of the perovskite solar cell. Therefore, the application can effectively reduce the recombination of electrons and holes, improve the extraction and transmission efficiency of holes, and enable more holes to be transmitted to one of the first electrode and the second electrode, thereby improving the open voltage and the current of the perovskite solar cell, and improving the photoelectric conversion efficiency and the service life of the perovskite solar cell.
In any embodiment of the present application, the difference avbm 1 between the top energy level of the valence band of the second hole transporting layer and that of the first hole transporting layer is-1.0 eV to 1.0eV. In the perovskite solar cell, the second hole transport layer and the first hole transport layer have proper valence band top energy level difference values, and the whole hole transport layer has proper energy level gradient, so that the perovskite solar cell is beneficial to reducing the recombination of electrons and holes, improving the extraction and transmission efficiency of holes and reducing energy loss. When the difference between the top energy levels of the valence bands of the second hole transport layer and the first hole transport layer is too large, excessive hole transition energy loss between the energy levels is caused. Optionally, the difference avbm 1 between the top energy level of the valence band of the second hole transport layer and the top energy level of the valence band of the first hole transport layer is between-0.3 eV and 0.3eV. The top energy level difference between the second hole transport layer and the first hole transport layer is smaller, which is favorable for further reducing the recombination of electrons and holes, improving the hole transport efficiency and reducing the energy loss.
In any embodiment of the present application, the first doping element includes at least one of an alkali metal element, an alkaline earth metal element, a transition metal element, and a halogen element. Optionally, the alkali metal element comprises at least one of Li, na, K, rb, cs. Optionally, the alkaline earth metal element comprises at least one of Be, mg, ca, sr, ba. Optionally, the transition metal element includes at least one of Ti, cr, mn, fe, co, ni, cu, zn, zr, nb, mo, ru, rh, pd, ag, cd, ta, pt, au. Optionally, the halogen element includes at least one of F, cl, br, I. After the nickel oxide is doped by the first doping element, the photoelectric characteristic of the first hole transport layer can be changed, so that the energy levels of the first hole transport layer and the light absorption layer are better matched, the hole extraction efficiency is improved, and the photoelectric conversion efficiency of the perovskite solar cell is finally improved.
In any embodiment of the present application, the mass percentage of the first doping element is 20% or less based on the total mass of the first hole transport material. Optionally, the mass percentage of the first doping element is 5% -15%. The selection of a suitable doping amount is advantageous for better adjustment of the band position of the first hole transport layer. The excessive mass percentage of the first doping element may damage the crystal structure of nickel oxide, cause a larger energy band structure deviation, and affect the hole extraction and transport capacity of the first hole transport layer.
In any embodiment of the application, the second hole transport material comprises at least one of the following materials doped or undoped with a second doping element: moO (MoO) 3 、CuO、Cu 2 O、CuI、NiMgLiO、CuGaO 2 、CuGrO 2 And CoO. The hole transport materials can better isolate water and oxygen, inhibit corrosion of the water and oxygen to the first hole transport material and improve hole transport efficiency.
In any embodiment of the present application, the second doping element includes at least one of an alkali metal element, an alkaline earth metal element, a transition metal element, a lean metal element, a metalloid element, a halogen element, a non-metal element, an ionic liquid, a carboxylic acid, phosphoric acid, a carbon derivative, a self-assembled single molecule, a polymer. Optionally, the alkali metal element comprises at least one of Li, na, K, rb, cs. Optionally, the alkaline earth metal element comprises at least one of Be, mg, ca, sr, ba. Optionally, the transition metal element includes at least one of Ti, cr, mn, fe, co, ni, cu, zn, zr, nb, mo, ru, rh, pd, ag, cd, ta, pt, au. Optionally, the lean metallic element comprises at least one of Al, ga, in, sn, tl, pb, bi. Optionally, the metalloid element comprises at least one of B, si, ge, as, sb, te. Optionally, the halogen element includes at least one of F, cl, br, I. Optionally, the nonmetallic element includes at least one of P, S, se. Optionally, the ionic liquid comprises 1-butyl-3-methylimidazole tetrafluoroborate and NH 4 Cl、(NH 4 ) 2 S, at least one of tetramethyl ammonium hydroxide aqueous solution and trifluoroethanol. Optionally, the carboxylic acid comprises at least one of ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, 4-imidazole acetic acid hydrochloride, acetic acid. Optionally, the carbon derivative comprises carbon quantum dots, carbon nanotubes, graphene, C 60 、g-C 3 N 4 、C 9 、NPC 60 -OH、DPC 60 At least one of them. Alternatively, the self-assembled single molecule comprises 2-phenethylamine hydrogenIodate, N-diethylaniline, 9-bis (4-aminophenyl) fluorene, 4-pyridine carboxylic acid, dopamine, 3-aminopropyl triethoxysilane, glycine. Optionally, the polymer comprises at least one of styrene, polyethylenimine, polyethylene oxide, tris (N, N-tetramethylene) phosphoramide.
By doping the second hole transport material, the energy band position of the second hole transport layer can be adjusted, so that the second hole transport layer and the first hole transport layer have proper valence band top energy level difference and proper energy level gradient, the recombination of electrons and holes is reduced, the extraction and transport efficiency of holes is improved, and the on-voltage and current of the perovskite solar cell are improved. The conductivity of the second hole transporting material can also be improved by doping it.
In any embodiment of the present application, the mass percentage of the second doping element is less than or equal to 30% based on the total mass of the second hole transport material. Optionally, the mass percentage of the second doping element is 5% -25%. The proper doping amount is favorable for better regulating the energy band position of the second hole transport layer, so that the second hole transport layer and the first hole transport layer have proper valence band top energy level difference and proper energy level gradient, the recombination of electrons and holes is reduced, and the extraction and transmission efficiency of the holes is improved.
In any embodiment of the present application, the difference Δvbm2 between the top energy levels of the valence bands of the first hole transport layer and the light absorbing layer is between-1.0 eV and 1.0eV. Optionally, the difference avbm 2 between the top energy level of the valence band of the first hole transporting layer and the light-absorbing layer is between-0.3 eV and 0.3eV. The difference in valence band top energy levels between the first hole transport layer and the light absorbing layer is in a suitable range to facilitate more efficient extraction of holes in the light absorbing layer by the first hole transport layer.
In any embodiment of the application, the difference between the conduction band top energy levels of the second hole transport layer and the light absorbing layer is greater than or equal to 0.5eV. The difference between the conduction band top energy levels of the second hole transport layer and the light absorbing layer is in a proper range, so that electron transport can be blocked and recombination of electrons and holes can be reduced.
In any embodiment of the application, the difference between the conduction band top energy levels of the first hole transport layer and the light absorbing layer is greater than or equal to 0.5eV. The difference between the conduction band top energy levels of the first hole transport layer and the light absorbing layer is in a proper range, so that electron transport can be blocked, and recombination of electrons and holes can be reduced.
In any embodiment of the application, the difference between the fermi level of the second hole transport layer and the top energy level of the valence band is less than or equal to 1.5eV. The difference between the fermi level of the second hole transport layer and the top level of the valence band is smaller, so that the second hole transport layer can have better P-type semiconductor characteristics, and the hole transport capacity is improved.
In any embodiment of the application, the difference between the fermi level of the first hole transport layer and the top energy level of the valence band is less than or equal to 1.5eV. The difference between the fermi level of the first hole transport layer and the top level of the valence band is smaller, so that the first hole transport layer can have better P-type semiconductor characteristics, and the extraction and transport capacity of holes can be improved.
In any embodiment of the application, the band gap of the second hole transport layer is ≡1.5eV. The second hole transmission layer with larger band gap can better filter ultraviolet light and reduce the damage of the ultraviolet light to the light absorption material.
In any embodiment of the application, the second hole transport layer has a thickness of 1nm to 300nm. Optionally, the thickness of the second hole transport layer is 1nm to 100nm.
In any embodiment of the application, the first hole transport layer has a thickness of 5nm to 1000nm. Alternatively, the first hole transport layer has a thickness of 10nm to 200nm.
In any embodiment of the present application, the ratio of the thickness of the first hole transport layer to the thickness of the second hole transport layer is 1:1 to 10:1. Compared with the first hole transport layer, the second hole transport layer is thinner, and the film is more compact and stable, so that the hole transport rate is improved.
In any embodiment of the application, the light absorbing layer comprises a perovskite material.
In any of the embodiments of the present application, one of the first electrode and the second electrode is a transparent electrode. Alternatively, the transparent electrode is an FTO electrode, or an ITO electrode.
In any embodiment of the present application, one of the first electrode and the second electrode is a metal electrode or a conductive carbon electrode. Optionally, the metal electrode is selected from one or more of gold electrode, silver electrode, aluminum electrode and copper electrode.
In any embodiment of the application, the perovskite solar cell further comprises an electron transport layer, the electron transport layer being located between the light absorbing layer and the second electrode or the first electrode, and the light absorbing layer being located between the first hole transport layer and the electron transport layer. The electron transport layer can reduce potential barrier between the electrode and the light absorption layer, promote electron transport, effectively block holes, and inhibit electron and hole recombination.
A second aspect of the application provides a photovoltaic module comprising the perovskite solar cell of the first aspect of the application.
The photovoltaic module comprises the perovskite solar cell provided by the application, and therefore has at least the same advantages as the perovskite solar cell.
In order to more clearly illustrate the technical solution of the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be briefly described below. It is apparent that the drawings described below are only some embodiments of the present application, and that other drawings may be obtained from the drawings without inventive work for those skilled in the art.
Fig. 1 is a schematic structural view of an embodiment of the perovskite solar cell of the present application.
Fig. 2 is a schematic structural view of another embodiment of the perovskite solar cell of the application.
Embodiments of the perovskite solar cell and the photovoltaic module according to the present application are specifically disclosed below in detail with reference to the accompanying drawings as appropriate. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided for a full understanding of the present application by those skilled in the art, and are not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments of the application, as well as alternative embodiments, may be combined with each other to form new solutions, unless otherwise specified, and such solutions should be considered to be included in the disclosure of the application.
All technical features and optional technical features of the application may be combined with each other to form new technical solutions, unless specified otherwise, and such technical solutions should be considered as included in the disclosure of the application.
All the steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
The perovskite solar cell is a solar cell which uses a perovskite material as a light absorption layer, sunlight is absorbed by the perovskite material immediately after entering the light absorption layer, and the energy of photons excites electrons originally bound around atomic nuclei to form free electrons, and the electrons can generate a hole at the same time after being excited, so that electron-hole pairs are formed. After the electron-hole pairs are separated into electrons and holes, the electrons and holes flow to the cathode and anode of the perovskite solar cell, respectively. Some carrier loss, such as electron and hole recombination, is inevitably accompanied during electron and hole transport. The hole transport layer is an important functional layer of the perovskite solar cell, plays roles in extracting and transporting holes, simultaneously blocking electrons and preventing the electrons and the holes from being combined, and is important for improving the photoelectric conversion efficiency of the perovskite solar cell.
The hole transport layer of perovskite solar cells typically employs nickel oxide NiO x As inorganic hole-transporting material, poly [ bis (4-phenyl) is used(2, 4, 6-trimethylphenyl) amine](Poly[bis(4-phenyl)(2,4,6-triMethylphenyl)aMine]PTAA) as an organic hole transport material, both materials are inexpensive and have high structural stability. Nickel oxide and PTAA also have suitable work functions and band sites to better match the energy level structure of the perovskite material in the light absorbing layer to ensure hole extraction and transport. However, nickel oxide and PTAA have poor surface wettability after film formation, affecting the quality of the film. In addition, ni in the bulk phase after nickel oxide film formation 3+ To make it capable of conducting holes, while the surface is present of part of Ni 3+ The NiO and the NiOOH are easy to react with oxygen in the environment, so that the resistivity of the surface layer of the hole transport layer is increased, and the extraction and the transport of holes are not facilitated. PTAA is a polymeric hole transport material, and has a generally high resistivity, which is also detrimental to hole extraction and transport.
In view of the above problems, the inventors have improved the structure of the hole transport layer.
A first aspect of an embodiment of the application provides a perovskite solar cell. Fig. 1 is a schematic structural view of an embodiment of the perovskite solar cell of the present application, and fig. 2 is a schematic structural view of another embodiment of the perovskite solar cell of the present application. As shown in fig. 1 and 2, the perovskite solar cell includes a first electrode 1, a second electrode 5, and a light absorbing layer 3 between the first electrode 1 and the second electrode 5, further includes a first hole transporting layer 21 and a second hole transporting layer 22, and the first hole transporting layer 21 is located between the second hole transporting layer 22 and the light absorbing layer 3. As shown in fig. 1, the second hole transport layer 22 is located between the first electrode 1 and the light absorbing layer 3. As shown in fig. 2, the second hole transport layer 22 is located between the second electrode 5 and the light absorbing layer 3.
The first hole transport material of the first hole transport layer 21 is selected from one of PTAA, nickel oxide doped or undoped with a first doping element. The second hole transport material of the second hole transport layer 22 is at least one selected from the group consisting of P-type transition metal oxide semiconductor materials and P-type transition metal halide semiconductor materials capable of blocking water and oxygen.
The first hole transport material is close to the light absorption layer, holes in the light absorption layer can be efficiently extracted, and the second hole transport material has better surface wettability and better film forming property, so that the bonding strength between the whole hole transport layer and an electrode (for example, a first electrode or a second electrode) is improved.
The second hole transport material can also form a passivation protection layer on the surface of the first hole transport layer to passivate the surface of the first hole transport layer to prevent the first hole transport material from being denatured or degraded by contact with air (e.g., part of Ni present on the nickel oxide surface) 3+ Easily reacts with oxygen in the environment to generate NiO and NiOOH) to affect the extraction and transport of holes by the first hole transport layer. The second hole transport material is selected from at least one of a P-type transition metal oxide semiconductor material and a P-type transition metal halide semiconductor material that is capable of sequestering water and oxygen, and therefore, the second hole transport material is also capable of inhibiting corrosion of the first hole transport material (e.g., PTAA, nickel oxide) by water and oxygen. Therefore, after the first hole transport layer and the second hole transport layer are combined, the extraction and transport capacity of the first hole transport layer to holes can be better exerted. Wherein Ni exists on the shallow surface of the nickel oxide film after the film formation 2+ And oxygen vacancies, which cause a decrease in the amount of charge and are detrimental to hole extraction and transport. The transition metal cations in the second hole transport material can diffuse into the shallow surface of the nickel oxide to a certain extent, and the effects of supplementing relevant charge loss and vacancies, passivating the surface of the nickel oxide and isolating water and oxygen are achieved, so that the extraction and transport capacity of the nickel oxide to holes can be better exerted.
After the passivation protection layer is formed on the surface of the nickel oxide, the second hole transport material can also reduce the resistivity of the surface of the nickel oxide, improve the overall conductivity of the surface of the first hole transport layer and the hole transport layer, and further improve the extraction and transport efficiency of holes. In addition, PTAA is a polymer hole transport material, and the resistivity is generally high, so that after the first hole transport layer and the second hole transport layer are combined, the overall conductivity of the hole transport layer can be improved, and further, the extraction and transport efficiency of holes can be improved.
The light absorbing material of perovskite solar cells is typically a halide perovskite material (e.g., an inorganic halide perovskite material, an organic halide perovskite material, or an organic-inorganic hybrid halide perovskite material), which has the advantages of a large carrier diffusion length, an easily adjustable band gap, high defect tolerance, and low manufacturing cost, and thus has received a great deal of attention. However, the halide perovskite material itself has poor stability, and is easily decomposed by water oxygen or the like, thereby accelerating the aging of the perovskite solar cell. The presence of Ion migration (Ion mobility) is another important property of halide perovskite materials, and migration and accumulation of charged ions can lead to significant changes in the doping concentration of the light-absorbing layer and the built-in electric field, and even to local crystal structure changes; ion migration and accumulation may also cause localized chemical doping effects that alter the fermi level of the ion accumulation region, bending the energy level, thereby affecting the separation, transport, and extraction of photogenerated carriers. The ion migration and the defect are closely related, and the crystal internal defects provide a movable path for ions, so that in the perovskite solar cell provided by the embodiment of the application, the crystal internal defects of the second hole transport material are fewer, and compared with the first hole transport layer, the second hole transport layer is more compact and stable, and can block further migration of charged halogen ions, so that the stability of the perovskite solar cell is improved.
Therefore, the perovskite solar cell provided by the application can effectively reduce the recombination of electrons and holes, improve the extraction and transmission efficiency of holes, and enable more holes to be transmitted to one of the first electrode and the second electrode, so that the open voltage and current of the perovskite solar cell are improved, and the photoelectric conversion efficiency and the service life of the perovskite solar cell are improved.
In some embodiments, the first hole transport material is selected from nickel oxide doped with a first doping element. After the nickel oxide is doped by the first doping element, the photoelectric characteristics of the first hole transport layer, such as transparency, energy band structure, work function, carrier density, conductivity and the like, can be changed, so that the energy levels of the first hole transport layer and the light absorption layer are better matched, the hole extraction efficiency is improved, and the photoelectric conversion efficiency of the perovskite solar cell is finally improved.
In some embodiments, the first doping element includes at least one of an alkali metal element, an alkaline earth metal element, a transition metal element, and a halogen element. The selection of a suitable first doping element is advantageous for better tuning of the band position of the first hole transport layer.
As an example, the alkali metal element includes at least one of Li, na, K, rb, cs. Optionally, the alkali metal element includes at least one of Li, na, K.
As an example, the alkaline earth metal element includes at least one of Be, mg, ca, sr, ba. Optionally, the alkaline earth metal element includes at least one of Be, mg, ca. Further, the alkaline earth metal element includes Mg.
As an example, the transition metal element includes at least one of Ti, cr, mn, fe, co, cu, zn, zr, nb, mo, ru, rh, pd, ag, cd, ta, pt, au. Optionally, the transition metal element includes at least one of Ti, cr, mn, fe, co, cu, mo. Further, the transition metal element includes at least one of Co and Cu.
As an example, the halogen element includes at least one of F, cl, br, I. Optionally, the halogen element includes at least one of F, cl.
The form of the first doping element is not particularly limited, and may be, for example, an atomic, molecular or ionic form. As an example, the precursor for forming the first doping element includes, but is not limited to, at least one of an alkali metal simple substance, an alkaline earth metal simple substance, a transition metal simple substance, a halogen simple substance, an alkali metal halide, an alkaline earth metal halide, a transition metal halide.
In some embodiments, the first doping element is present in an amount of 20% by mass or less based on the total mass of the first hole transport material. For example, the first doping element may be present in an amount of 0%,1%,2%,3%,4%,5%,6%,7%,8%,9%,10%,11%,12%,13%,14%,15%,16%,17%,18%,19%,20% or more by mass. Optionally, the mass percentage of the first doping element is 1% -20%, 2% -20%, 3% -20%, 4% -20%, 5% -20%, 1% -15%, 2% -15%, 3% -15%, 4% -15%, 5% -15%, 1% -10%, 2% -10%, 3% -10%, 4% -10%, 1% -5%, 2% -5%, 3% -5%, or 4% -5%. The selection of a suitable doping amount is advantageous for better adjustment of the band position of the first hole transport layer. The excessive mass percentage of the first doping element may damage the crystal structure of nickel oxide, cause a larger energy band structure deviation, and affect the hole extraction and transport capacity of the first hole transport layer.
The first doping element and the content thereof can be selected according to the requirement, and the first doping element can be one type or a combination of a plurality of types.
In some embodiments, the second hole transport material of the second hole transport layer 22 comprises at least one of the following materials doped or undoped with a second doping element: moO (MoO) 3 、CuO、Cu 2 O、CuI、NiMgLiO、CuGaO 2 、CuGrO 2 And CoO. The hole transport materials can better isolate water and oxygen, inhibit corrosion of the water and oxygen to the first hole transport materials (such as PTAA and nickel oxide) and improve hole transport efficiency. The transition metal cations of the hole transport materials have the radius close to that of nickel ions, can better diffuse into the shallow surface of nickel oxide, and have the effects of supplementing relevant charge loss and vacancies, passivating the surface of nickel oxide and isolating water and oxygen.
Optionally, the second hole transport material of the second hole transport layer 22 comprises at least one of the following materials doped or undoped with a second doping element: moO (MoO) 3 CuI, and NiMgLiO.
In some embodiments, the second hole transport material is doped with a second doping element. By doping the second hole transport material, the energy band position of the second hole transport layer can be adjusted, so that the second hole transport layer and the first hole transport layer have proper valence band top energy level difference and proper energy level gradient, the recombination of electrons and holes is reduced, the extraction and transport efficiency of holes is improved, and the on-voltage and current of the perovskite solar cell are improved. The conductivity of the second hole transporting material can also be improved by doping it.
In some embodiments, the second doping element includes at least one of an alkali metal element, an alkaline earth metal element, a transition metal element, a lean metal element, a metalloid element, a halogen element, a non-metal element, an ionic liquid, a carboxylic acid, phosphoric acid, a carbon derivative, a self-assembled single molecule, a polymer. The selection of a suitable second doping element facilitates better adjustment of the band position of the second hole transport layer.
As an example, the alkali metal element includes at least one of Li, na, K, rb, cs. Optionally, the alkali metal element includes at least one of Li, na, K.
As an example, the alkaline earth metal element includes at least one of Be, mg, ca, sr, ba. Optionally, the alkaline earth metal element includes at least one of Be, mg, ca. Further, the alkaline earth metal element includes Mg.
As an example, the transition metal element includes at least one of Ti, cr, mn, fe, co, ni, cu, zn, zr, nb, mo, ru, rh, pd, ag, cd, ta, pt, au. Optionally, the transition metal element includes at least one of Ti, cr, mn, fe, co, ni, cu, mo. Further, the transition metal element includes at least one of Co and Cu.
As an example, the lean metal element includes at least one of Al, ga, in, sn, tl, pb, bi. Optionally, the lean metal element includes at least one of Al and Ga. Further, the lean metal element includes Al.
As an example, the metalloid element includes at least one of B, si, ge, as, sb, te. Optionally, the metalloid element comprises at least one of B, sb. Further, the metalloid element includes B.
As an example, the halogen element includes at least one of F, cl, br, I. Optionally, the halogen element includes at least one of F, cl.
As an example, the nonmetallic element includes at least one of P, S, se. Optionally, the nonmetallic element includes P.
As an example, the ionic liquid includes 1-Butyl-3-methylimidazole tetrafluoroborate (1-Butyl-3-methylimidazolium tetrafluoroborate, BMIMBF 4 )、NH 4 Cl、(NH 4 ) 2 S, tetramethyl ammonium hydroxide aqueous solution (Tetramethylammonium hydroxide aqueous solution, TMAH), trifluoroethanol (trifluorethanol). Optionally, the ionic liquid comprises BMIMBF 4 、NH 4 At least one of Cl. Further, the ionic liquid comprises NH 4 Cl。
As an example, the carboxylic acid includes at least one of ethylenediamine tetraacetic acid (Ethylenediaminetetraacetic acid, EDTA), diethylenetriamine pentaacetic acid (Diethylenetriaminepentaacetic acid, DTPA), 4-imidazole acetic acid hydrochloride (imagci), acetic acid. Alternatively, the carboxylic acid comprises EDTA.
As examples, the carbon derivatives include carbon quantum dots, carbon nanotubes, graphene, C 60 、g-C 3 N 4 、C 9 、NPC 60 -OH、DPC 60 At least one of them. Optionally, the carbon derivative comprises a carbon quantum dot.
As an example, the self-assembled single molecule includes at least one of 2-phenethylamine hydroiodate (2-Phenylethylamine Hydroiodide, PEAI), N-Diethylaniline (DEA), 9-Bis (4-aminophenyl) Fluorene (FDA), 4-pyridinecarboxylic acid, dopamine (Dopamine), 3-Aminopropyltriethoxysilane (APTES), glycine (Glycine). Optionally, the self-assembled single molecule comprises at least one of PEAI, DEA, FDA, dopamine. Further, the self-assembled single molecule comprises PEAI.
As an example, the polymer includes at least one of Polystyrene (PS), polyethyleneimine (PEIE), polyethylene oxide (PEO), tris (N, N-tetramethylene) phosphoramide (TPPO). Optionally, the polymer comprises PEIE.
The form of the second doping element is not particularly limited, and may be, for example, an atomic, molecular or ionic form. As an example, the precursor for forming the second doping element includes, but is not limited to, at least one of an alkali metal simple substance, an alkaline earth metal simple substance, a transition metal simple substance, a lean metal simple substance, a metalloid simple substance, a halogen simple substance, a non-metal simple substance, an ionic liquid, a carboxylic acid, phosphoric acid, a carbon derivative, a self-assembled single molecule, a polymer, an alkali metal halide, an alkaline earth metal halide, a transition metal halide, a lean metal halide, a metalloid halide.
In some embodiments, the second doping element is present in an amount of 30% by mass or less based on the total mass of the second hole transport material. For example, the second doping element may be 0%,1%,2%,3%,4%,5%,6%,7%,8%,9%,10%,11%,12%,13%,14%,15%,16%,17%,18%,19%,20%,21%,22%,23%,24%,25%,26%,27%,28%,29%,30% or more by mass. Optionally, the mass percentage of the second doping element is 1% -30%, 2% -30%, 3% -30%, 4% -30%, 5% -30%, 1% -25%, 2% -25%, 3% -25%, 4% -25%, 5% -25%, 1% -20%, 2% -20%, 3% -20%, 4% -20%, 5% -20%, 1% -15%, 2% -15%, 3% -15%, 4% -15%, 5% -15%, 1% -10%, 2% -10%, 3% -10%, 4% -10%, 1% -5%, 2% -5%, 3% -5%, or 4% -5%. The proper doping amount is favorable for better regulating the energy band position of the second hole transport layer, so that the second hole transport layer and the first hole transport layer have proper valence band top energy level difference and proper energy level gradient, the recombination of electrons and holes is reduced, and the extraction and transport efficiency of the holes is improved. The second doping element is excessively high in mass percentage, so that the crystal structure of the second hole transport material is possibly damaged, and the larger energy band structure deviation is caused, so that the performance of the second hole transport layer is influenced.
The second doping element and the content thereof can be selected according to the requirement, and the second doping element can be one or a combination of a plurality of types.
In some embodiments, the difference Δvbm1 in valence band top energy levels between the second hole transport layer 22 and the first hole transport layer 21 is between-1.0 eV and 1.0eV. In perovskite solar cells, efficient transport of holes is dependent on a good energy level match between the light absorbing layer/hole transporting layer. In the perovskite solar cell of the embodiment of the application, the hole transport layer has a proper energy level gradient as a whole, and the difference DeltaVBM 1 between the valence band top energy levels of the second hole transport layer and the first hole transport layer is between-1.0 eV and 1.0eV. When the second hole transmission layer and the first hole transmission layer have proper valence band top energy level difference values, the recombination of electrons and holes can be effectively reduced, the extraction and transmission efficiency of holes can be improved, more holes can be transmitted to one of the first electrode and the second electrode, the voltage and the current of the perovskite solar cell can be further improved, the photoelectric conversion efficiency of the perovskite solar cell can be improved, and the service life of the perovskite solar cell can be prolonged. When the difference between the valence band top energy levels of the second hole transport layer and the first hole transport layer is too large, excessive transition energy loss of holes between energy levels is caused, for example, in some cases, excessive phonons may be generated, and the thermal stability of the perovskite solar cell is influenced while charge energy is lost.
In some embodiments, the difference in valence band top energy level avbm 1 between the second hole transport layer 22 and the first hole transport layer 21 is from-0.8 eV to 0.8eV, -0.7eV, -0.6eV, -0.5eV, -0.4eV, or-0.3 eV. The top energy level difference between the second hole transport layer and the first hole transport layer is smaller, which is favorable for further reducing the recombination of electrons and holes, improving the hole transport efficiency and reducing the energy loss.
In some embodiments, the difference avbm 2 between the top energy level of the valence band of the first hole transport layer 21 and the light-absorbing layer 3 is between-1.0 eV and 1.0eV. Alternatively, the difference ΔVBM2 in the top energy level of the valence band of the first hole transport layer 21 and the light absorbing layer 3 is-0.8 eV to 0.8eV, -0.7eV to 0.7eV, -0.6eV to 0.6eV, -0.5eV to 0.5eV, -0.4eV to 0.4eV, or-0.3 eV to 0.3eV. The difference in valence band top energy levels between the first hole transport layer and the light absorbing layer is in a suitable range to facilitate more efficient extraction of holes in the light absorbing layer by the first hole transport layer.
In some embodiments, the difference between the conduction band top energy level of the second hole transport layer 22 and the light absorbing layer 3 is greater than or equal to 0.5eV. The difference between the conduction band top energy levels of the second hole transport layer and the light absorbing layer is in a proper range, so that electron transport can be blocked and recombination of electrons and holes can be reduced.
In some embodiments, the difference between the conduction band top energy levels of the first hole transport layer 21 and the light absorbing layer 3 is greater than or equal to 0.5eV. The difference between the conduction band top energy levels of the first hole transport layer and the light absorbing layer is in a proper range, so that electron transport can be blocked, and recombination of electrons and holes can be reduced.
In some embodiments, the difference between the fermi level of the second hole transport layer 22 and the top energy level of the valence band is less than or equal to 1.5eV. The difference between the fermi level of the second hole transport layer and the top level of the valence band is smaller, so that the second hole transport layer can have better P-type semiconductor characteristics, and the hole transport capacity is improved.
In some embodiments, the difference between the fermi level of the first hole transport layer 21 and the top energy level of the valence band is 1.5eV or less. The difference between the fermi level of the first hole transport layer and the top level of the valence band is smaller, so that the first hole transport layer can have better P-type semiconductor characteristics, and the extraction and transport capacity of holes can be improved.
In some embodiments, the band gap of the second hole transport layer 22 is ≡1.5eV. The larger bandgap second hole transport layer is better able to filter ultraviolet light, reducing the damage of ultraviolet light to light absorbing materials (e.g., perovskite materials).
The thickness of the first hole transport layer 21 is not particularly limited and may be selected according to practical requirements. In some embodiments, the thickness of the first hole transport layer 21 is 5nm to 1000nm. Alternatively, the thickness of the first hole transport layer 21 is 10nm to 200nm.
The thickness of the second hole transport layer 22 is not particularly limited and may be selected according to practical requirements. In some embodiments, the thickness of the second hole transport layer 22 is 1nm to 300nm. Alternatively, the thickness of the second hole transport layer 22 is 1nm to 100nm.
In some embodiments, the ratio of the thickness of the first hole transport layer 21 to the thickness of the second hole transport layer 22 is 1:1 to 10:1. Optionally, the ratio of the thickness of the first hole transport layer 21 to the thickness of the second hole transport layer 22 is 1.5:1 to 10:1,2:1 to 10:1,3:1 to 10:1,4:1 to 10:1, or 5:1 to 10:1. Compared with the first hole transport layer, the second hole transport layer is thinner, and the film is more compact and stable, so that the hole transport rate is improved.
In some embodiments, the light absorbing layer 3 comprises a perovskite material. Perovskite materials as intrinsic semiconductor materials can transport both electrons and holes, and therefore can act as both light absorbing and electron or hole transporting layers in perovskite solar cells.
The type of perovskite material is not particularly limited and may be selected according to actual requirements. In some embodiments, the perovskite material may comprise one or more of an inorganic halide perovskite material, an organic-inorganic hybrid halide perovskite material. The perovskite material may have a molecular formula of ABX 3 A represents an inorganic cation, an organic cation, or an organic-inorganic mixed cation, B represents an inorganic cation, an organic cation, or an organic-inorganic mixed cation, and X represents an inorganic anion, an organic anion, or an organic-inorganic mixed anion.
As an example, A is selected from CH 3 NH 3 + (MA + )、CH(NH 2 ) 2 + (FA + )、Li + 、Na + 、K + 、Rb + 、Cs + One or more of them. Alternatively, A is selected from CH 3 NH 3 + 、CH(NH 2 ) 2 + 、Cs + One or more of the above-mentioned materials,
as a means ofExemplary, B is selected from Pb 2+ 、Sn 2+ 、Be 2+ 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Ba 2+ 、Zn 2+ 、Ge 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ One or more of them. Alternatively, B is selected from Pb 2+ 、Sn 2+ One or both of the above-mentioned materials,
by way of example, X is selected from F - 、Cl - 、Br - 、I - One or more of them. Alternatively, X is selected from Cl - 、Br - 、I - One or more of them.
In some embodiments, the perovskite material includes, but is not limited to, CH 3 NH 3 PbI 3 (MAPbI 3 )、CH(NH 2 ) 2 PbI 3 (FAPbI 3 )、CsPbI 3 ，CsPbI 2 Br、CsPbIBr 2 One or more of them.
In some embodiments, the thickness of the light absorbing layer 3 is 50nm to 2000nm.
In some embodiments, the material of the first electrode 1 is not particularly limited, and may be selected according to actual requirements. For example, the material of the first electrode 1 is an organic conductive material, an inorganic conductive material, or an organic-inorganic mixed conductive material.
In some embodiments, the material of the second electrode 5 is not particularly limited, and may be selected according to actual requirements. For example, the material of the second electrode 5 is an organic conductive material, an inorganic conductive material, or an organic-inorganic mixed conductive material.
In some embodiments, one of the first electrode 1 and the second electrode 5 is a transparent electrode. In some embodiments, the first electrode 1 and the second electrode 5 are transparent electrodes. Optionally, the transparent electrode is FTO (fluorine doped tin dioxide, snO) 2 F) electrode, ITO (indium doped tin dioxide, snO) 2 :In 2 O 3 ) An electrode, AZO (aluminum doped zinc oxide) electrode, BZO (boron doped zinc oxide) electrode, or IZO (indium zinc oxide) electrode. Optionally, the transparent electrode is an FTO electrode, or an ITO electrode.
In some embodiments, one of the first electrode 1, the second electrode 5 is a metal electrode, or a conductive carbon electrode. Optionally, the metal electrode is selected from one or more of a gold electrode, a silver electrode, an aluminum electrode and a copper electrode.
In some embodiments, the thickness of the first electrode 1 is not particularly limited, and may be selected according to practical requirements. For example, 50nm to 1000nm.
In some embodiments, the thickness of the second electrode 5 is not particularly limited, and may be selected according to practical requirements. For example, 10nm to 500nm.
As shown in fig. 1 and 2, in some embodiments, the perovskite solar cell further comprises an electron transport layer 4. The electron transport layer 4 is located between the light absorbing layer 3 and the second electrode 5 or the first electrode 1, and the light absorbing layer 3 is located between the first hole transport layer 21 and the electron transport layer 4. The electron transport layer can reduce potential barrier between the electrode and the light absorption layer, promote electron transport, effectively block holes, and inhibit electron and hole recombination.
In some embodiments, the thickness of the electron transport layer 4 is not particularly limited, and may be selected according to practical requirements. For example, 20nm to 300nm.
In some embodiments, the electron transport material of the electron transport layer 4 is not particularly limited, and may be selected according to practical requirements. For example, the electron transport material is selected from an organic electron transport material, an inorganic electron transport material, or an organic-inorganic hybrid electron transport material.
As an example, the electron transport material is selected from at least one of the following materials: imide compounds, quinone compounds, fullerenes and derivatives thereof, 2', 7' -tetra (N, N-P-methoxyanilino) -9,9' -spirobifluorene (Spiro-OMeTAD), methoxy triphenylamine-fluoro formamidine (OMeTPA-FA), poly (3, 4-ethylenedioxythiophene) polystyrene sulfonic acid (PEDOT: PSS), poly 3-hexylthiophene (P3 HT), triphenylamine (H101) with triptycene as core,3, 4-ethylene dioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N- (4-aniline) carbazole-spirobifluorene (CzPAF-SBF), polythiophene, metal oxide (metal element selected from Mg, ni, cd, zn, in, pb, mo, W, sb, bi, cu, hg, ti, ag, mn, fe, V, sn, zr, sr, ga, or Cr), silicon oxide (SiO) 2 ) Strontium titanate (SrTiO) 3 ) Calcium titanate (CaTiO) 3 ) Lithium fluoride (LiF), calcium fluoride (CaF) 2 ) Copper thiocyanate (CuSCN).
Optionally, the electron transport material is selected from one or more of fullerenes and derivatives thereof. For example, the electron transport material is selected from PC 60 BM、PC 70 One or more of BM. The conduction band bottom energy level of the fullerene and the derivative thereof can be better matched with the conduction band bottom energy level of the light absorption layer, so that the extraction and transmission of electrons are promoted.
In some embodiments, the perovskite solar cell comprises a first electrode 1, a second hole transport layer 22, a first hole transport layer 21, a light absorbing layer 3, an electron transport layer 4, and a second electrode 5, which are arranged in this order. The difference avbm 1 between the valence band top energy level of the second hole transport layer 22 and the first hole transport layer 21 is-1.0 eV to 1.0eV, the first hole transport material of the first hole transport layer 21 is selected from PTAA, doped or undoped nickel oxide with a first doping element, and the second hole transport material of the second hole transport layer 22 comprises at least one of the following materials doped or undoped with a second doping element: moO (MoO) 3 CuI, and NiMgLiO.
In some embodiments, the perovskite solar cell comprises a first electrode 1, an electron transport layer 4, a light absorbing layer 3, a first hole transport layer 21, a second hole transport layer 22, and a second electrode 5, which are arranged in this order. The difference avbm 1 between the valence band top energy level of the second hole transport layer 22 and the first hole transport layer 21 is-1.0 eV to 1.0eV, the first hole transport material of the first hole transport layer 21 is selected from PTAA, doped or undoped nickel oxide with a first doping element, and the second hole transport material of the second hole transport layer 22 comprises at least one of the following materials doped or undoped with a second doping element: moO (MoO) 3 CuI, and NiMgLiO.
The perovskite solar cell according to the first aspect of the embodiment of the present application is not limited to the above-described structure, and may further include other functional layers. For example, in some embodiments, the perovskite solar cell further comprises a hole blocking layer located between the light absorbing layer and the electron transporting layer. In some embodiments, the perovskite solar cell further comprises an electrode modification layer for modifying the first electrode or the second electrode, wherein the electrode modification layer can reduce an energy level barrier between the light absorbing layer and the first electrode or the second electrode, and plays a role of transporting holes to block electrons or transporting electrons to block holes.
Perovskite solar cells may be prepared according to methods known in the art. An exemplary method of preparation includes the steps of: preparing a first electrode, forming a second hole transport layer on the first electrode, forming a first hole transport layer on the second hole transport layer, forming a light absorbing layer on the first hole transport layer, forming an electron transport layer on the light absorbing layer, and forming a second electrode on the electron transport layer. Another exemplary method of preparation comprises: preparing a first electrode, forming an electron transport layer on the first electrode, forming a light absorbing layer on the electron transport layer, forming a first hole transport layer on the light absorbing layer, forming a second hole transport layer on the first hole transport layer, and forming a second electrode on the second hole transport layer.
The film forming method of each film layer is not particularly limited, and film forming methods known in the art, such as chemical bath deposition, chemical vapor deposition, electrochemical deposition, physical epitaxial growth, thermal evaporation, atomic layer deposition, precursor liquid slit coating, precursor liquid knife coating, sol-gel method, magnetron sputtering, pulsed laser deposition, and the like, may be employed.
The energy band distribution of each film layer can be measured by an X-ray photoelectron spectrometer (XPS) and an ultraviolet electron spectrometer (UPS).
The perovskite solar cell of the first aspect of the present application may be used alone as a single junction perovskite solar cell, or may be formed as a stacked solar cell with a perovskite or other type of solar cell, such as a perovskite-perovskite stacked solar cell, or a perovskite-crystalline silicon stacked solar cell.
Photovoltaic module
The second aspect of the embodiment of the application also provides a photovoltaic module, which comprises the perovskite solar cell of the first aspect of the embodiment of the application, and the perovskite solar cell can be used as a power supply of the photovoltaic module after the processes of series-parallel connection, encapsulation and the like.
In some embodiments, the photovoltaic module comprises a single junction perovskite solar cell, perovskite-perovskite tandem solar cell, or perovskite-crystalline silicon tandem solar cell of the first aspect of the application.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1
Preparing an ITO electrode:
taking a group of glass substrates with specification of 2.0cm multiplied by 2.0cm and covered with ITO, respectively cleaning the surfaces of the glass substrates with acetone and isopropanol for 2 times, immersing the glass substrates into deionized water for ultrasonic treatment for 10min, drying the glass substrates in a blast drying oven, and placing the glass substrates in a glove box (N) 2 Atmosphere).
Preparing a second hole transport layer:
adding KCl into CuI chlorobenzene solution with concentration of 0.08mol/L to prepare precursor solution, wherein the concentration of KCl is 3g/L, spin-coating the precursor solution on the obtained ITO glass substrate at the speed of 5000-6500 rpm, and heating at 300 ℃ for 15min on a constant temperature hot table to obtain a second hole transport layer with thickness of 10 nm.
Preparing a first hole transport layer:
spin-coating NiO having a concentration of 3wt% on the obtained second hole transport layer at a speed of 4000rpm to 6000rpm x The aqueous solution of the nano-colloid is heated at 300 ℃ for 60min on a constant temperature hot table, and a first hole transport layer with the thickness of 15nm is obtained.
Preparing a light absorption layer:
spin-coating MAPbI having a concentration of 1.5mol/L on the resulting first hole transport layer at a speed of 3000rpm to 4500rpm 3 Dimethylformamide solution, then heated at 100℃for 30min on a constant temperature hot plate, cooled to room temperature, and a light-absorbing layer having a thickness of 800nm was obtained.
Preparing an electron transport layer:
PC with a concentration of 20mg/mL was spin-coated on the light absorbing layer obtained at a speed of 800rpm to 1500rpm 60 BM chlorobenzene solution, then heated at 100℃for 10min on a constant temperature hot plate, gives an electron transport layer with a thickness of 60 nm.
Preparing an Ag electrode:
placing the above sample into vacuum coater at 5×10 -4 And evaporating an Ag electrode with the thickness of 100nm on the surface of the obtained electron transport layer under the vacuum condition of Pa.
Example 1 the final perovskite solar cell structure was ITO/doped CuI/NiO x /MAPbI 3 /PC 60 BM/Ag。
Example 2
Preparing an ITO electrode:as in example 1.
Preparing a second hole transport layer:
adding KI into a CuI aqueous solution with the concentration of 0.08mol/L to prepare a precursor solution, wherein the concentration of KI is 3g/L, spin-coating the precursor solution on the obtained ITO glass substrate at the speed of 5000-6500 rpm, and heating at 300 ℃ for 15min on a hot bench to obtain a second hole transport layer with the thickness of 10 nm.
Preparation of the first hole transport layer
A PTAA toluene solution having a concentration of 2mg/mL was spin-coated on the obtained second hole transport layer at a speed of 4000rpm to 6000rpm, followed by heating at 100℃for 10 minutes on a constant temperature heat stage, to obtain a first hole transport layer having a thickness of 15 nm.
Preparing a light absorption layer:as in example 1.
Preparing an electron transport layer:as in example 1.
Preparing an Ag electrode:as in example 1.
Example 2 the final perovskite solar cell structure was ITO/doped CuI/PTAA/MAPbI 3 /PC 60 BM/Ag。
Example 3
Preparing an ITO electrode:as in example 1.
Preparation of the second hole transport layer
At a MoO concentration of 0.08mol/L 3 Adding KCl into chlorobenzene solution to prepare precursor solution, wherein the concentration of KCl is 3g/L, spin-coating the precursor solution on the obtained ITO glass substrate at the speed of 5000-6500 rpm, and heating at 300 ℃ for 15min on a constant temperature heat table to obtain a second hole transport layer with the thickness of 10 nm.
Preparation of the first hole transport layer
Spin-coating NiO having a concentration of 3wt% on the obtained second hole transport layer at a speed of 4000rpm to 6000rpm x The aqueous solution of the nano-colloid is heated at 300 ℃ for 60min on a constant temperature hot table, and a first hole transport layer with the thickness of 15nm is obtained.
Preparing a light absorption layer:as in example 1.
Preparing an electron transport layer:as in example 1.
Preparing an Ag electrode:as in example 1.
Example 3 the final perovskite solar cell structure was ITO/doped MoO 3 /NiO x /MAPbI 3 /PC 60 BM/Ag。
Example 4
Preparing an ITO electrode:as in example 1.
Preparing a second hole transport layer:
at a MoO concentration of 0.08mol/L 3 Adding KCl into the colloid aqueous solution to prepare a precursor solution, wherein the concentration of the KCl is 3g/L, spin-coating the precursor solution on the obtained ITO glass substrate at a speed of 5000-6500 rpm, and heating at 300 ℃ for 15min on a constant temperature heat table to obtain a second hole transport layer with a thickness of 10 nm.
Preparation of the first hole transport layer
A PTAA toluene solution having a concentration of 2mg/mL was spin-coated on the obtained second hole transport layer at a speed of 4000rpm to 6000rpm, followed by heating at 100℃for 10 minutes on a constant temperature heat stage, to obtain a first hole transport layer having a thickness of 15 nm.
Preparing a light absorption layer:as in example 1.
Preparing an electron transport layer:as in example 1.
Preparing an Ag electrode:as in example 1.
Example 4 the final perovskite solar cell structure was ITO/doped MoO 3 /PTAA/MAPbI 3 /PC 60 BM/Ag。
Example 5
Preparing an ITO electrode:as in example 1.
Preparation of the second hole transport layer
KCl is added into NiMgLiO chlorobenzene solution with concentration of 0.08mol/L to prepare precursor solution, wherein the concentration of KCl is 3g/L, the precursor solution is spin-coated on the obtained ITO glass substrate at the speed of 5000 rpm-6500 rpm, and then the precursor solution is heated on a constant temperature heat table at 300 ℃ for 15min, so that a second hole transport layer with thickness of 10nm is obtained.
Preparation of the first hole transport layer
Spin-coating NiO having a concentration of 3wt% on the obtained second hole transport layer at a speed of 4000rpm to 6000rpm x The aqueous solution of the nano-colloid is heated at 300 ℃ for 60min on a constant temperature hot table, and a first hole transport layer with the thickness of 15nm is obtained.
Preparing a light absorption layer:as in example 1.
Preparing an electron transport layer:as in example 1.
Preparing an Ag electrode:as in example 1.
Example 5 the final perovskite solar cell structure was ITO/doped NiMgLiO/NiO x /MAPbI 3 /PC 60 BM/Ag。
Example 6
Preparing an ITO electrode:as in example 1.
Preparing a second hole transport layer:
KCl is added into NiMgLiO colloid aqueous solution with concentration of 0.08mol/L to prepare precursor solution, wherein the concentration of KCl is 3g/L, the precursor solution is spin-coated on the obtained ITO glass substrate at the speed of 5000 rpm-6500 rpm, and then the precursor solution is heated on a constant temperature heat table at 300 ℃ for 15min, so that a second hole transport layer with the thickness of 10nm is obtained.
Preparing a first hole transport layer:
a PTAA toluene solution having a concentration of 2mg/mL was spin-coated on the obtained second hole transport layer at a speed of 4000rpm to 6000rpm, followed by heating at 100℃for 10 minutes on a constant temperature heat stage, to obtain a first hole transport layer having a thickness of 15 nm.
Preparing a light absorption layer:as in example 1.
Preparing an electron transport layer:as in example 1.
Preparing an Ag electrode:as in example 1.
Example 6 the final perovskite solar cell structure was ITO/doped NiMgLiO/PTAA/MAPbI 3 /PC 60 BM/Ag。
Example 7
Preparing an ITO electrode:as in example 1.
Preparing a second hole transport layer:
at a MoO concentration of 0.08mol/L 3 Adding lithium carbonate into the colloid aqueous solution to prepare a precursor solution, wherein the concentration of the lithium carbonate is 10%, spin-coating the precursor solution on the obtained ITO glass substrate at a speed of 5000-6500 rpm, and heating at 300 ℃ for 15min on a constant temperature heat table to obtain a second hole transport layer with a thickness of 10 nm.
Preparing a first hole transport layer:
a PTAA toluene solution having a concentration of 2mg/mL was spin-coated on the obtained second hole transport layer at a speed of 4000rpm to 6000rpm, followed by heating at 100℃for 10 minutes on a constant temperature heat stage, to obtain a first hole transport layer having a thickness of 15 nm.
Preparing a light absorption layer:as in example 1.
Preparing an electron transport layer:as in example 1.
Preparing an Ag electrode:as in example 1.
EXAMPLE 7 bestThe structure of the finally prepared perovskite solar cell is ITO/doped MoO 3 /PTAA/MAPbI 3 /PC 60 BM/Ag。
Example 8
Preparing an ITO electrode:as in example 1.
Preparing a second hole transport layer:
at a MoO concentration of 0.08mol/L 3 Adding lithium carbonate into the colloid aqueous solution to prepare a precursor solution, wherein the concentration of the lithium carbonate is 6%, spin-coating the precursor solution on the obtained ITO glass substrate at a speed of 5000-6500 rpm, and heating at 300 ℃ for 15min on a constant temperature heat table to obtain a second hole transport layer with a thickness of 10 nm.
Preparing a first hole transport layer:
spin-coating NiO having a concentration of 3wt% on the obtained second hole transport layer at a speed of 4000rpm to 6000rpm x The aqueous solution of the nano-colloid is heated at 300 ℃ for 60min on a constant temperature hot table, and a first hole transport layer with the thickness of 15nm is obtained.
Preparing a light absorption layer:as in example 1.
Preparing an electron transport layer:as in example 1.
Preparing an Ag electrode:as in example 1.
Example 8 the final perovskite solar cell structure was ITO/doped MoO 3 /NiO x /MAPbI 3 /PC 60 BM/Ag。
Example 9
Preparing an ITO electrode: As in example 1.
Preparing a second hole transport layer:
at a concentration of 0.08mol/L Cu 2 Addition of CoCl to aqueous O-colloid solution 2 The precursor solution is prepared and then prepared,wherein CoCl 2 The precursor solution was spin-coated on the obtained ITO glass substrate at a speed of 5000rpm to 6500rpm, and then heated at 300℃for 15 minutes on a constant temperature heat stage, to obtain a second hole transport layer having a thickness of 10 nm.
Preparing a first hole transport layer:
a PTAA toluene solution having a concentration of 2mg/mL was spin-coated on the obtained second hole transport layer at a speed of 4000rpm to 6000rpm, followed by heating at 100℃for 10 minutes on a constant temperature heat stage, to obtain a first hole transport layer having a thickness of 15 nm.
Preparing a light absorption layer:as in example 1.
Preparing an electron transport layer:as in example 1.
Preparing an Ag electrode:as in example 1.
Example 9 the final perovskite solar cell structure was ITO/doped Cu 2 O/PTAA/MAPbI 3 /PC 60 BM/Ag。
Example 10
Preparing an ITO electrode:as in example 1.
Preparing a second hole transport layer:
at a concentration of 0.08mol/L Cu 2 Addition of CoCl to aqueous O-colloid solution 2 Preparing a precursor solution, wherein the CoCl 2 The precursor solution was spin-coated on the obtained ITO glass substrate at a speed of 5000rpm to 6500rpm, and then heated at 300℃for 15 minutes on a constant temperature heat stage, to obtain a second hole transport layer having a thickness of 10 nm.
Preparing a first hole transport layer:
spin-coating NiO having a concentration of 3wt% on the obtained second hole transport layer at a speed of 4000rpm to 6000rpm x The nano colloid aqueous solution is heated at 300 ℃ for 60min on a constant temperature hot table to obtain the thicknessA first hole transport layer of 15 nm.
Preparing a light absorption layer:as in example 1.
Preparing an electron transport layer:as in example 1.
Preparing an Ag electrode:as in example 1.
Example 10 the final perovskite solar cell structure was ITO/doped Cu 2 O/NiO x /MAPbI 3 /PC 60 BM/Ag。
Comparative example 1
Preparing an ITO electrode:as in example 1.
Preparation of hole transport layer
NiO with a concentration of 6wt% was spin-coated on the obtained ITO glass substrate at a speed of 4000rpm to 6000rpm x -CuI mixed chlorobenzene solution, wherein the mass ratio of nickel oxide to CuI is 1:1, followed by heating at 300 ℃ for 60min on a constant temperature hot bench, to obtain a hole transport layer with a thickness of 25 nm.
Preparing a light absorption layer:as in example 1.
Preparing an electron transport layer:as in example 1.
Preparing an Ag electrode:as in example 1.
Comparative example 1 the perovskite solar cell structure finally produced was ITO/NiO x +CuI/MAPbI 3 /PC 60 BM/Ag。
Comparative example 2
Preparing an ITO electrode:as in example 1.
Preparing a hole transport layer:
a PTAA-CuI mixed chlorobenzene solution with a concentration of 2mg/mL was spin-coated on the obtained ITO glass substrate at a speed of 4000 rpm-6000 rpm, wherein the mass ratio of PTAA to CuI was 1:1, followed by heating at 100℃for 15min on a constant temperature heat stage, to obtain a hole transport layer with a thickness of 25 nm.
Preparing a light absorption layer:as in example 1.
Preparing an electron transport layer:as in example 1.
Preparing an Ag electrode:as in example 1.
Comparative example 2 the perovskite solar cell structure finally produced was ITO/PTAA+CuI/MAPbI 3 /PC 60 BM/Ag。
Comparative example 3
Preparing an ITO electrode:as in example 1.
Preparing a second hole transport layer:
a vanadium (iso) oxide isopropanol solution was spin-coated on the obtained ITO glass substrate at a speed of 5000rpm to 6500rpm, followed by heating at 120℃for 15 minutes on a constant temperature heat table, to obtain a second hole transport layer having a thickness of 10 nm.
Preparing a first hole transport layer:
spin-coating NiO having a concentration of 3wt% on the obtained second hole transport layer at a speed of 4000rpm to 6000rpm x The aqueous solution of the nano-colloid is heated at 300 ℃ for 60min on a constant temperature hot table, and a first hole transport layer with the thickness of 15nm is obtained.
Preparing a light absorption layer:as in example 1.
Preparing an electron transport layer:as in example 1.
Preparing an Ag electrode:as in example 1.
Comparative example 3 the perovskite solar cell structure finally produced was ITO/V 2 O 5 /NiO x /MAPbI 3 /PC 60 BM/Ag。
Test part
The band distributions of the hole transporting layer and the light absorbing layer obtained were measured at normal temperature and pressure using an X-ray photoelectron spectrometer (XPS) model Escalab 250Xi (from Thermo Scientific), and the results are shown in table 1.
Table 2 shows the test results of the open circuit voltage Voc, the short circuit current density Jsc, the Fill Factor (Fill Factor), and the power conversion Efficiency (Efficiency) of the perovskite solar cells prepared in examples 1 to 10 and comparative examples 1 to 3 under standard simulated solar irradiation (am1.5g).
TABLE 1
TABLE 2
| Sequence number | Voc(V) | Jsc(mA/cm 2 ) | Fill Factor(％) | Efficiency(％) |
| Example 1 | 1.15 | 23.6 | 75.5 | 20.5 |
| Example 2 | 1.13 | 23.4 | 75.6 | 20.0 |
| Example 3 | 1.14 | 23.5 | 75.8 | 20.3 |
| Example 4 | 1.08 | 23.2 | 75.8 | 19.0 |
| Example 5 | 1.12 | 23.4 | 75.5 | 19.8 |
| Example 6 | 1.10 | 23.4 | 75.8 | 19.5 |
| Example 7 | 1.02 | 20.7 | 70.5 | 14.9 |
| Example 8 | 1.05 | 20.4 | 72.3 | 15.5 |
| Example 9 | 1.06 | 20.8 | 72.5 | 16.0 |
| Example 10 | 1.04 | 20.5 | 71.2 | 15.2 |
| Comparative example 1 | 0.95 | 20.0 | 57.9 | 11.0 |
| Comparative example 2 | 0.93 | 19.0 | 59.4 | 10.5 |
| Comparative example 3 | 0.98 | 19.8 | 58.1 | 11.3 |
As can be seen from the test results of table 2, the perovskite solar cells prepared in examples 1 to 10 have higher open circuit voltage Voc, short circuit current density Jsc, fill factor, and power conversion efficiency as compared to comparative example 1 and comparative example 2.
As can also be seen from the test results of Table 2, comparative document 3 uses V 2 O 5 As the second hole transporting material, however, the prepared perovskite solar cell had inferior performance to examples 1 to 10. The possible reason is that V at normal temperature 2 O 5 Slightly soluble in water and has certain hygroscopicity; in addition, V 2 O 5 As a strong oxidant, it is extremely easily consumed by the reaction of the reducing agent in the environment to form a powder or mesoporous state without encapsulation, thereby additionally introducing water oxygen in the environment into the perovskite solar cell, and thus, water oxygen cannot be well isolated. In addition, V 2 O 5 The lattice matching degree with nickel oxide is also not ideal, and the protection and passivation effect on the first hole transport layer are poor, so that the interface impedance and defect density between the first hole transport layer and the second hole transport layer are high, and the extraction and transport of holes are affected.
While the application has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made and equivalents will be apparent to those skilled in the art without departing from the scope of the application. Therefore, the protection scope of the application is subject to the protection scope of the claims.
Claims (17)
- A perovskite solar cell comprising:a first electrode;a second electrode; anda light absorbing layer between the first electrode and the second electrode,wherein,the perovskite solar cell further comprises a first hole transport layer and a second hole transport layer, the first hole transport layer is positioned between the second hole transport layer and the light absorption layer, wherein the second hole transport layer is positioned between the first electrode and the light absorption layer, or the second hole transport layer is positioned between the second electrode and the light absorption layer,The first hole transport material of the first hole transport layer is selected from one of PTAA and nickel oxide doped or undoped with a first doping element,the second hole transport material of the second hole transport layer comprises at least one of a P-type transition metal oxide semiconductor material and a P-type transition metal halide semiconductor material which can isolate water and oxygen.
- The perovskite solar cell of claim 1, wherein the difference avbm 1 between the top energy level of the valence band of the second hole transporting layer and the first hole transporting layer is between-1.0 eV and 1.0eV, optionally between-0.3 eV and 0.3eV.
- The perovskite solar cell according to claim 1 or 2, wherein the first doping element comprises at least one of an alkali metal element, an alkaline earth metal element, a transition metal element, and a halogen element,optionally, the alkali metal element comprises at least one of Li, na, K, rb, cs,optionally, the alkaline earth metal element comprises at least one of Be, mg, ca, sr, ba,optionally, the transition metal element comprises at least one of Ti, cr, mn, fe, co, ni, cu, zn, zr, nb, mo, ru, rh, pd, ag, cd, ta, pt, au,optionally, the halogen element includes at least one of F, cl, br, I.
- A perovskite solar cell according to any one of claims 1 to 3, wherein the mass percentage of the first doping element is less than or equal to 20%, optionally 5% to 15%, based on the total mass of the first hole transport material.
- The perovskite solar cell of any one of claims 1-4, wherein the second hole transport material comprises at least one of the following materials doped or undoped with a second doping element: moO (MoO) 3 、CuO、Cu 2 O、CuI、NiMgLiO、CuGaO 2 、CuGrO 2 And CoO.
- The perovskite solar cell of claim 5 wherein the second doping element comprises at least one of an alkali metal element, an alkaline earth metal element, a transition metal element, a lean metal element, a metalloid element, a halogen element, a non-metal element, an ionic liquid, a carboxylic acid, phosphoric acid, a carbon derivative, a self-assembled single molecule, a polymer,optionally, the alkali metal element comprises at least one of Li, na, K, rb, cs,optionally, the alkaline earth metal element comprises at least one of Be, mg, ca, sr, ba,optionally, the transition metal element comprises at least one of Ti, cr, mn, fe, co, ni, cu, zn, zr, nb, mo, ru, rh, pd, ag, cd, ta, pt, au,Optionally, the lean metal element comprises at least one of Al, ga, in, sn, tl, pb, bi,optionally, the metalloid element comprises at least one of B, si, ge, as, sb, te,optionally, the halogen element comprises at least one of F, cl, br, I,optionally, the nonmetallic element includes at least one of P, S, se,optionally, the ionic liquid comprises 1-butyl-3-methylimidazole tetrafluoroborate and NH 4 Cl、(NH 4 ) 2 S, tetramethyl ammonium hydroxide aqueous solution, triAt least one of the fluoroethanol and the fluorine-containing ethanol,optionally, the carboxylic acid comprises at least one of ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, 4-imidazole acetic acid hydrochloride and acetic acid,optionally, the carbon derivative comprises carbon quantum dots, carbon nanotubes, graphene, C 60 、g-C 3 N 4 、C 9 、NPC 60 -OH、DPC 60 At least one of the above-mentioned materials,optionally, the self-assembled single molecule comprises at least one of 2-phenethylamine hydroiodidate, N-diethylaniline, 9-bis (4-aminophenyl) fluorene, 4-pyridine carboxylic acid, dopamine, 3-aminopropyl triethoxysilane and glycine,optionally, the polymer comprises at least one of styrene, polyethylenimine, polyethylene oxide, tris (N, N-tetramethylene) phosphoramide.
- A perovskite solar cell according to claim 5 or 6, wherein the mass percentage of the second doping element is less than or equal to 30%, optionally 5% -25%, based on the total mass of the second hole transport material.
- The perovskite solar cell according to any one of claims 1-7, wherein the difference avbm 2 in valence band top energy level of the first hole transporting layer and the light absorbing layer is-1.0 eV, optionally-0.3 eV.
- The perovskite solar cell according to any one of claims 1-8, wherein,the difference value of the conduction band top energy level of the second hole transport layer and the light absorption layer is more than or equal to 0.5eV, and/or,the difference value of the conduction band top energy level of the first hole transport layer and the light absorption layer is more than or equal to 0.5eV.
- The perovskite solar cell according to any one of claims 1-9, wherein,the difference between the fermi level of the second hole transport layer and the top level of the valence band is less than or equal to 1.5eV, and/or,the difference between the Fermi level of the first hole transport layer and the top level of the valence band is less than or equal to 1.5eV.
- The perovskite solar cell according to any one of claims 1 to 10, wherein the band gap of the second hole transport layer is ≡1.5eV.
- The perovskite solar cell according to any one of claims 1-11, wherein,the second hole transport layer has a thickness of 1nm to 300nm, alternatively 1nm to 100nm, and/or,the thickness of the first hole transport layer is 5nm to 1000nm, alternatively 10nm to 200nm,optionally, the ratio of the thickness of the first hole transport layer to the thickness of the second hole transport layer is 1:1 to 10:1.
- The perovskite solar cell according to any one of claims 1-12, wherein the light absorbing layer comprises a perovskite material.
- The perovskite solar cell according to any one of claims 1-13, wherein one of the first electrode, the second electrode is a transparent electrode, optionally the transparent electrode is an FTO electrode, or an ITO electrode.
- A perovskite solar cell according to any one of claims 1 to 14, wherein one of the first electrode, the second electrode is a metal electrode, or a conductive carbon electrode, optionally the metal electrode is selected from one or more of a gold electrode, a silver electrode, an aluminium electrode, a copper electrode.
- The perovskite solar cell according to any one of claims 1-15, wherein the perovskite solar cell further comprises an electron transport layer, the electron transport layer is located between the light absorbing layer and the second electrode or the first electrode, and the light absorbing layer is located between the first hole transport layer and the electron transport layer.
- A photovoltaic module comprising a perovskite solar cell according to any one of claims 1-16.
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